Antiviral composite resin composition having excellent virus inactivation function and composite resin-coated steel sheet using same

Abstract

The present invention provides an antiviral composite resin composition comprising: 30-60 wt% of a urethane-modified polyester binder resin; 3-15 wt% of a curing agent; 0.1 to 10% by weight of a pigment; 0.1 to 10% by weight of an antiviral compound; the antiviral compound comprises one or more selected from (A) a metal hydroxide ([M1 (OH) 2]), (B) hydroxyapatite ([Ca10 (PO4) 6 (OH) 2]) and (C) a metal-doped thermosensitive titanium dioxide photocatalyst ([M2-TiO2]), M1 is Ca or Mg, and M2 is Pt, Cr, V, Mn, Fe, Zn, Cu, Ni, Zr, Mo, Ag, W or Au.

Description

Technical Field

[0001] The present invention relates to a composite resin composition having antiviral properties capable of killing viruses such as coronaviruses, and a composite resin-coated steel plate having excellent virus killing function using the composite resin composition. Background Art

[0002] Recently, due to the global pandemic caused by the coronavirus (Covid-19), not only are socioeconomic problems serious, but there is also an urgent need to develop vaccines or therapeutic agents. Recently, the coronavirus that has caused a global pandemic has evolved into SARS in 2013, MERS in 2016, and Covid-19 in 2019. In addition, Covid-19 has mutated from Alpha, Beta, Gamma, Delta to the recent pandemic Omicron, which has a fatal impact on human health and health care. Coronavirus contains RNA nucleic acid in an outer shell composed of spherical phospholipids and proteins. Most viruses penetrate into host cells of humans or animals and multiply by using the ribosomes of host cells to replicate nucleic acids in large quantities. The size of the virus is smaller than that of bacteria or molds, and the virus can spread and replicate quickly, and it mutates quickly and has strong transmission power, so there is a problem that it is difficult to develop a therapeutic agent or vaccine.

[0003] In addition, it is reported that copper metal surface, nano metal or metal ion, quaternary ammonium ion have killing function to virus. It is reported that, with regard to copper metal, the nano metal dissolved from the surface penetrates into the shell of bacteria or virus, makes them lose the replication function, thereby kills bacteria or virus, and it is reported that metal ions such as Ag, Ni, Zn also kill bacteria or virus based on similar mechanism. It is reported that, with regard to the macromolecule comprising quaternary ammonium, the inherent hydrophobic functional group combines with the shell of bacteria or virus and destroys its function, thereby kills bacteria or virus. But, when using metal ion as above as coating, it is difficult to dissolve ion fully, or when long-term use, due to oxidation and discoloration, effect tends to weaken or disappear. In addition, with regard to the killing action brought by organic compound, when the surface of treatment material, not only its effect is incomplete, and there is the problem of being toxic to human body, so its use is restricted.

[0004] In particular, in composite coated steel sheets for household appliances and building materials, in order to be used for a long time for more than 10 years, the coating thickness is usually made to be several microns (μm) to tens of microns or more. Therefore, in the case of the above-mentioned metals, when the liquid phase coating solution is applied to the steel plate, due to the density, the possibility of being present inside the coating is high, so there is a problem of difficulty in exerting functionality on the surface. In addition, when used for a long time, such as copper metal, there is a problem of surface color change due to oxidation. In addition, when using quaternary ammonium, although some effects are shown, the immediate effect is insufficient and incomplete, so its use is limited.

[0005] As part of efforts to address the harmful environment caused by viruses as described above, it is necessary to develop a special surface treatment product that can impart a function of inactivating viruses, particularly coronaviruses, to the surface of steel plates, which are essential materials in our lives.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] Korean Patent Publication No. 10-2020-0047666 Summary of the invention

[0009] 1. Technical issues to be resolved

[0010] In order to solve the above technical problems, an object of the present invention is to provide a coating composition, which will not change color even after long-term use, and uses inorganic compounds that are easy to float to the surface of the coating film due to their lower density than metal particles, thereby having the function of killing microorganisms on the surface of the coating film.

[0011] Another object of the present invention is to provide a coated steel sheet using the coating composition having antiviral properties as described above.

[0012] (II) Technical solution

[0013] According to one embodiment of the present invention, an antiviral composite resin composition is provided, comprising: 30-60 wt % of a urethane modified polyester binder resin; 3-15 wt % of a curing agent; 0.1-10 wt % of a pigment; 0.1-10 wt % of an antiviral compound; and the remainder of a solvent, wherein the antiviral compound comprises a metal hydroxide ([M1(OH)2]), (B) a hydroxyapatite ([Ca 10 (PO4)6(OH)2]) and (C) one or more metal-doped thermosensitive titanium dioxide photocatalysts ([M2-TiO2]), wherein M1 is Ca or Mg, and M2 is Pt, Cr, V, Mn, Fe, Zn, Cu, Ni, Zr, Mo, Ag, W or Au.

[0014] According to another embodiment of the present invention, an antiviral composite resin coated steel plate is provided, comprising: a base steel plate; and an antiviral composite resin coating film, wherein the antiviral composite resin coating film is located on at least one side of the base steel plate, and the antiviral composite resin coating film comprises an antiviral composite resin composition.

[0015] (III) Beneficial effects

[0016] According to the present invention, an antiviral composite resin composition is provided, wherein the antiviral composite resin composition is a composition in which an inorganic oxide having the function of killing viruses and a thermosensitive photocatalyst are dispersed in a polymer resin composition. The coating formed by the composition of the present invention has the function of effectively killing the virus adsorbed on the surface of the coating in the form of droplets, i.e., water containing the virus, through the hydroxide anions and active oxygen generated in the coating. In particular, it is characterized in that due to the strong cation and anion dissolution characteristics of the inorganic hydroxide and the complementary effect of the thermosensitive photocatalyst activated by infrared rays even in a lightless place, it is easy to adsorb droplets containing viruses and easily kill viruses. In addition, it has the advantage that even if the steel plate for building materials is used for a long time, the characteristics of the antiviral substance will not change significantly. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a diagram schematically showing the cross section of the antiviral composite resin coated steel plate provided by the present invention and the virus killing principle of the antiviral composite resin coated steel plate. Best Mode for Carrying Out the Invention

[0018] Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0019] According to one embodiment of the present invention, a composite resin composition is provided, which contains a specified pigment and an antiviral substance in a transparent resin composition composed of a urethane-modified polyester polymer resin, a curing agent, and a solvent. In the case of a coating film formed by coating with the resin composition of the present invention, the antiviral substance with a small specific gravity can float to the interface during curing, thereby forming a coating film with excellent antiviral properties.

[0020] According to one embodiment of the present invention, the antiviral composite resin composition can provide a coating film with excellent processability and chemical resistance. By forming a urethane-modified polyester resin coating film mixed with a pigment and an antiviral compound, the above-mentioned components can form a composite network structure, thereby providing excellent stamping processability and surface functionality.

[0021] To this end, in the antiviral composite resin composition according to one embodiment of the present invention, relative to the total weight of the resin composition, it may include: 30-60 weight % of urethane modified polyester resin; 3-15 weight % of curing agent; 0.1-10 weight % of pigment; 0.1-10 weight % of antiviral compound; and the balance of solvent.

[0022] For example, in an antiviral composite resin composition according to one embodiment of the present invention, relative to the total weight of the resin composition, it may include: 40-60 wt % of a urethane-modified polyester resin; 5-15 wt % of a curing agent; 5-8 wt % of a pigment; 1-8 wt % of an antiviral compound; and the remainder of a solvent.

[0023] Hereinafter, each component of the resin composition of the present invention will be described in more detail.

[0024] <Binder Resin>

[0025] The antiviral composite resin composition according to one embodiment of the present invention may use a urethane-modified polyester resin as a binder resin of the coating film. The urethane-modified polyester resin imparts excellent processability and chemical resistance to the coating film when cured.

[0026] The urethane-modified polyester resin may have a weight average molecular weight (MW) of 2,000 to 30,000.

[0027] Preferably, the weight average molecular weight (MW) of the urethane-modified polyester resin may be 5,000 to 25,000.

[0028] When the molecular weight of the urethane modified polyester resin is less than 2000, the chemical resistance and processability of the coating film are insufficient, and when the molecular weight of the urethane modified polyester resin exceeds 30000, the storage stability and operability of the solution may be deteriorated. The urethane modified polyester resin may use a urethane modified polyester resin having a glass transition temperature of 0-70°C.

[0029] In addition, the urethane-modified polyester resin may preferably have a hydroxyl value of 10 to 300, more preferably 20 to 200.

[0030] When the hydroxyl value of the urethane-modified polyester resin exceeds 300, the chemical resistance of the coating film may be reduced, and when the hydroxyl value of the urethane-modified polyester resin is less than 10, the crosslinking property of the coating film may be reduced.

[0031] In addition, the urethane modified polyester resin may have an acid value of 5-30 mgKOH / g, preferably an acid value of 10-25 mgKOH / g. When the acid value of the urethane modified polyester resin exceeds 30, the chemical resistance of the coating film may be reduced, and when the acid value of the urethane modified polyester resin is less than 10, the crosslinking property of the coating film may be reduced.

[0032] The content of the urethane-modified polyester resin may be 30-60% by weight, more preferably 40-60% by weight, relative to the entire antiviral composite resin composition. When the content of the urethane-modified polyester resin is not within the above range, the drying property of the coating film during curing may be reduced, and other physical properties may be reduced.

[0033] <Curing Agent>

[0034] The antiviral composite resin composition according to one embodiment of the present invention may use one or more selected from aziridine curing agents, melamine curing agents, and isocyanate curing agents as a curing agent for curing the binder resin.

[0035] The curing agent has excellent reactivity, and although not particularly limited, for example, an aziridine curing agent of the following structural formula (a) can be used.

[0036]

[0037] In the structural formula (a), R may be -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2OH or -CH2CH2OH, and the aziridine curing agent may be used alone or in combination of two or more.

[0038] Furthermore, the melamine-based curing agent of the present invention may use iminomelamine of the following structural formula (b) or methylated melamine of the following structural formula (c).

[0039]

[0040]

[0041] The melamine curing agent is not limited thereto, and at least one selected from the group consisting of iminomelamine of the structural formula (b) and methylated melamine of the structural formula (c) can be used.

[0042] Compared with methylated melamine, iminomelamine has a faster curing reaction speed, so it is conducive to high-speed curing, and as the content of iminomelamine increases, the degree of curing increases, thereby improving the hardness of the coating film. In addition, the curing speed of fully substituted methylated melamine is slow, but the smoothness of the coating film is improved, so it can provide excellent surface quality.

[0043] Therefore, the antiviral composite resin composition according to one embodiment of the present invention can improve the surface quality of the coating film by using methylated melamine as a curing agent, and can increase the reaction speed by adding iminomelamine with a fast reaction speed. Preferably, the iminomelamine of the structural formula (b) and the methylated melamine of the structural formula (c) can be mixed and used in a weight ratio of 1:1 to 1:4.

[0044] Furthermore, as the isocyanate curing agent of the present invention, an isocyanate curing agent such as a monoisocyanate of the following structural formula (d) or a diisocyanate of the following structural formula (e) can be used.

[0045] (d)

[0046] (e)

[0047] The isocyanate curing agent may be a monoisocyanate of structural formula (d) or a diisocyanate of structural formula (e).

[0048] In the structural formula (d), R may be methyl, ethyl, propyl, phenyl, 2-isopropylphenyl or cyclohexyl.

[0049] In the structural formula (e), R' can be 1,3-phenylene, 1,4-phenylene, tolylene-2,4, tolylene-2,6, m-xylylene, dicyclohexylmethane 4,4', methylenediphenyl 4,4', hexamethylene, etc.

[0050] The above isocyanate curing agents may be used alone or in combination of two or more.

[0051] The content of the curing agent may be 3-15% by weight, more preferably 5-15% by weight, relative to the entire antiviral composite resin composition. When the content of the curing agent is less than 3% by weight, the processability may be deteriorated due to insufficient curing, and when the content of the curing agent exceeds 15% by weight, the coating film may be easily cracked or broken due to over-curing.

[0052] <Pigment>

[0053] The antiviral composite resin composition according to one embodiment of the present invention may include a pigment having a unique color. In addition, when the antiviral composite resin coated steel sheet according to another embodiment of the present invention further includes a primer coating film, the primer coating film may also include a pigment.

[0054] The antiviral composite resin composition according to the present invention can have a unique color, especially a unique color formed by a combination of black pigment, red pigment and white pigment. Yellow pigment or light yellow pigment can be used in the primer coating film, but is not limited thereto.

[0055] By mixing the above-mentioned black pigment, red pigment, yellow pigment, and white pigment in a prescribed ratio, various colors can be realized.

[0056] The content of the pigment may be 0.1-10 wt %, more preferably 5-8 wt %, relative to the entire antiviral composite resin composition.

[0057] When the content of the pigment is less than 0.1 wt %, it may be difficult to obtain high hiding power and fine color of the steel plate, and when the content of the pigment exceeds 10 wt %, the viscosity of the solution increases so that workability may decrease and it may be difficult to obtain a fine surface appearance.

[0058] In addition, the base coating film may contain 1 to 8 wt % of a pigment based on the total weight of the base coating film.

[0059] As examples of the black pigment, carbon black, carbon nanotubes, graphite, graphene, etc. can be listed, and the pigment can include at least one selected from ferric oxide (Fe2O3), titanium dioxide (TiO2), carbon black, carbon nanotubes, graphite and graphene. In the present invention, as a red pigment, ferric oxide (Fe2O3) can be listed. Iron oxide has non-toxicity and chemical stability, and has the advantage of being able to present various colors. In the present invention, as an example of a white pigment, titanium dioxide (TiO2) can be listed. In the present invention, as an example of a yellow pigment, strontium chromate (StrontiumChromate) can be listed.

[0060] The pigment preferably has low oil absorption. The oil absorption of the pigment may be less than 60%, preferably in the range of 5-50%.

[0061] In addition, the average particle size (particle diameter) of the color pigment is preferably in the range of the dry coating thickness ±5 μm. For example, the average particle size (particle diameter) of the color pigment may be in the range of 5-30 μm.

[0062] In addition, in the antiviral composite resin composition according to one embodiment of the present invention, in addition to the colored pigment, an antirust pigment for enhancing the rust resistance of the coating film may be further included. The antirust pigment may be one or more selected from colloidal silica, silica sol and alkali metal silicate.

[0063] <Antiviral Compounds>

[0064] The antiviral composite resin composition according to one embodiment of the present invention may include an antiviral compound.

[0065] The antiviral compound may be selected from (A) metal hydroxide (represented by the formula [M1(OH)2], wherein M1 is Ca or Mg), (B) hydroxyapatite (represented by the formula [Ca 10 (PO4)6(OH)2]) and (C) metal-doped thermosensitive titanium dioxide photocatalyst (represented by the formula [M2-TiO2], wherein M2 is one or more of Pt, Cr, V, Mn, Fe, Zn, Cu, Ni, Zr, Mo, Ag, W or Au).

[0066] It is known that metal-doped titanium dioxide exhibits visible light or thermosensitive photocatalyst properties based on the following principle. Generally, TiO2 photocatalysts require 3.1eV of light energy. However, when a special metal or metal oxide is doped in the TiO2, it can be photoactive in a low energy region. The antiviral composite resin composition according to one embodiment of the present invention may include thermosensitive TiO2, which is photoactivated by visible light and infrared light by using a TiO2 photocatalyst doped with a metal oxide.

[0067] The antiviral compound may be used alone as one selected from the group consisting of (A) metal hydroxide, (B) hydroxyapatite and (C) metal-doped thermosensitive titanium dioxide photocatalyst.

[0068] In addition, if Figure 1 As shown, the antiviral compound may include a combination of two or more selected from (A) metal hydroxide, (B) hydroxyapatite and (C) metal-doped thermosensitive titanium dioxide photocatalyst.

[0069] For example, the antiviral compound may use a combination of one selected from the (A) metal hydroxide and (B) hydroxyapatite and an active oxygen (C) metal-doped thermosensitive titanium dioxide photocatalyst.

[0070] The (C) metal-doped thermosensitive titanium dioxide photocatalyst generates free radical species, and thus can exert more excellent antiviral performance when combined with one selected from (A) metal hydroxide and (B) hydroxyapatite.

[0071] When the weight ratio of the (C) metal-doped thermosensitive titanium dioxide photocatalyst to the (A) metal hydroxide or (B) hydroxyapatite is 3:1 to 1:3, the most effective antiviral properties can be exhibited.

[0072] In addition, the antiviral compound of the present invention can simultaneously contain (A) metal hydroxide, (B) hydroxyapatite and (C) metal-doped thermosensitive titanium dioxide photocatalyst. When the weight ratio of the (A) metal hydroxide, (B) hydroxyapatite and (C) metal-doped thermosensitive titanium dioxide photocatalyst is 1:1:1, the antiviral property can be shown to be excellent similar to that of the embodiment.

[0073] The content of the antiviral compound may be 0.1-10 wt %, more preferably 1-8 wt %, relative to the entire antiviral composite resin composition. When the content of the antiviral compound is less than 0.1 wt %, the virus killing rate is low, so the problem of insufficient effect may occur, and when the content of the antiviral compound exceeds 10 wt %, the processability of the coating may deteriorate.

[0074] <Remainder of solvent>

[0075] In the antiviral composite resin composition according to one embodiment of the present invention, the balance other than the above-mentioned mixed components may be a solvent.

[0076] In addition, the primer coating composition for forming the primer coating film may also contain a residual amount of solvent. The solvent contained in the primer coating composition may be the same as or different from the solvent used in the antiviral composite resin composition.

[0077] The solvent may be, for example, a solvent composed of one or more selected from toluene, xylene, isopropyl alcohol, solvent naphtha, cellosolve, cellosolve acetate, and butyl cellosolve. The solvent may be one or a mixture of two or more.

[0078] The viscosity of the composition can be changed according to the content of the solvent, but the content of the solvent added to each of the above compositions can be appropriately adjusted as needed, and is not particularly limited in the present invention. For example, in the case of an antiviral composite resin composition, considering the coating amount and adhesion, for example, the amount of viscosity can be adjusted to a degree that it takes 20-200 seconds to discharge from a DIN cup (DIN, 53211).

[0079] In the antiviral composite resin composition according to one embodiment of the present invention, in order to further improve the physical properties of the coating film, in addition to the above-mentioned components, one or more additives such as wax, curing catalyst, anti-pigment aggregation agent, defoaming agent, and leveling agent may be further included as needed. Any of the above-mentioned additives can also be appropriately used in the present invention as long as they are commonly used additives, and the additives can be applied according to conventional mixing ratios.

[0080] The preparation method of the antiviral composite resin composition according to one embodiment of the present invention is not particularly limited, but for example, a curing agent can be dispersed in a urethane-modified polyester resin as a binder resin to prepare a resin composition, and then a pigment for color and rust resistance and an antiviral compound are further added and dispersed and then placed in a solvent to prepare the antiviral composite resin composition.

[0081] <Antiviral composite resin coated steel sheet>

[0082] According to another embodiment of the present invention, an antiviral composite resin coated steel plate is provided, wherein the antiviral composite resin coated steel plate comprises a coating film formed by the antiviral composite resin composition of the present invention. When describing the antiviral composite resin coated steel plate, all descriptions for the antiviral composite resin composition can be applied in the same manner.

[0083] The antiviral composite resin-coated steel sheet can be provided by applying the antiviral composite resin composition as described above on at least one of one side (first side) and the other side (second side) of a base steel sheet.

[0084] The base steel sheet may be a galvanized steel sheet. Examples of the galvanized steel sheet are not limited thereto, but for example, a hot-dip galvanized steel sheet (GI), an alloyed hot-dip galvanized steel sheet (GA), an electrogalvanized steel sheet (EG), an aluminum-plated steel sheet, or a zinc-aluminum-magnesium ternary alloy-plated steel sheet may be used.

[0085] The antiviral composite resin coating film on the base steel plate is formed by the provided antiviral composite resin composition, which may include the urethane-modified polyester resin, melamine curing agent, pigment and antiviral compound as described above.

[0086] The composition of the antiviral composite resin coating film can be prepared by using the composition as described above comprising 30-60 wt % of urethane-modified polyester resin, 3-15 wt % of curing agent, 0.1-10 wt % of pigment, 0.1-10 wt % of antiviral compound and the balance of solvent.

[0087] For example, in the antiviral composite resin composition provided for the manufacture of the antiviral composite resin coated steel plate of the present invention, it may include, relative to the total weight of the resin composition: 40-60 weight % of urethane modified polyester resin; 5-15 weight % of curing agent; 5-8 weight % of pigment; 1-8 weight % of antiviral compound; and the remainder of solvent.

[0088] The antiviral composite resin composition can be coated on a base steel plate and then dried to form an antiviral composite resin coating. At this time, the coating method and the drying method are not particularly limited and can be performed by any method generally known in the art. Although drying is not limited thereto, it can be performed by, for example, a hot air heating method, an infrared heating method, an induction heating method, a natural drying method, etc.

[0089] More specifically, the antiviral composite resin composition according to one embodiment of the present invention is preferably dried at a metal peak temperature (PMT) of 180-260° C. Although not limited thereto, specifically, for example, in the case of a hot air heating method, the composition may be dried by hot air treatment at an atmospheric temperature of 200-340° C. for 10-50 seconds.

[0090] The antiviral composite resin coating film may be formed to have a dry coating film thickness of 3-40 μm, and preferably may be formed to have a dry coating film thickness of 5-30 μm.

[0091] When the dry film thickness of the antiviral composite resin coating is less than 5 μm, the color, hiding power, processability and solvent resistance of the composite resin coating may be reduced. When the dry film thickness of the antiviral composite resin coating exceeds 30 μm, the manufacturing cost may increase and the productivity may be reduced, so it is not preferred.

[0092] <Primer coating film>

[0093] According to another embodiment of the present invention, an antiviral composite resin coated steel plate may be an antiviral composite resin coated steel plate having a primer coating formed on at least one or both sides and an antiviral composite resin coating provided as a specific embodiment of the present invention formed on one side of the primer coating.

[0094] In the case of a steel sheet including the antiviral composite resin coating film (top coating film), a primer coating film may be located as a base coating film between the base steel sheet and the antiviral composite resin coating film (top coating film).

[0095] In the antiviral composite resin coated steel plate according to another embodiment of the present invention, there is no particular restriction on the primer coating further formed on the first surface and / or the second surface of the base steel plate. The primer coating improves the adhesion between the base steel plate and the antiviral composite resin coating and gives the steel plate other physical properties required for the steel plate, such as paintability and corrosion resistance. The primer coating can be any known coating in the technical field that can be applied between the base steel plate and the antiviral composite resin coating (top coating).

[0096] For example, the primer coating composition used to form the primer coating may be a composition consisting of 40-60 wt % of polyethylene polymer resin, 5-15 wt % of melamine curing agent, 1-8 wt % of colloidal silica, 1-8 wt % of pigment and the remainder of solvent. The remainder of solvent may be different from or the same as the solvent used as the remainder of solvent in the antiviral composite resin composition.

[0097] In addition, the primer coating film may be applied to a dry film thickness of 2-7 μm, preferably 3-5 μm. When the thickness of the primer coating film exceeds 7 μm, the manufacturing cost may increase and the productivity may decrease, which is not preferred. When the thickness of the primer coating film is 2 μm or less, it may be difficult to ensure the above-mentioned quality characteristics.

[0098] The primer coating is a coating that realizes the covering, rust prevention and color of the material, and is beneficial in improving the color, covering power, processability and corrosion resistance of the antiviral composite resin coating.

[0099] In another embodiment of the present invention, when the antiviral composite resin coating is formed only on one side of the base steel plate, considering the processability and corrosion resistance of the steel plate, it is preferred to form a resin coating on one side of the base steel plate where the composite resin coating is not formed. DETAILED DESCRIPTION

[0100] Example

[0101] The present invention will be described in more detail below by way of examples. However, the following examples are merely examples of specific embodiments of the present invention, and the present invention is not limited thereto.

[0102] Examples 1 to 27 and Comparative Examples 1 to 9

[0103] The urethane-modified polyester resin, curing agent, pigment, antiviral compound and the remaining amount of solvent are mixed according to the contents shown in Examples 1 to 27 and Comparative Examples 1 to 9 in the following [Table 1], and then dispersed using a high-speed bead mill disperser to prepare an antiviral composite resin composition.

[0104] As the urethane-modified polyester resin, a resin having a weight average molecular weight of 16,000 to 20,000 (manufactured by KCC Corporation, having a glass transition temperature (Tg) of 10 to 30° C.) was used.

[0105] As the curing agent, trimethylolpropane tris(β-N-aziridinyl) propionate was used as an aziridine-based curing agent, hexamethoxymethylmelamine was used as a melamine-based curing agent, and toluene diisocyanate was used as an isocyanate curing agent.

[0106] As the pigment, carbon black (Printex TM Series) as a black pigment, ferric oxide as a red pigment, and titanium dioxide as a white pigment.

[0107] As the antiviral compound, (A) calcium hydroxide (Ca(OH)2) or (B) hydroxyapatite (OSSGEN Co., Ltd.) as the metal hydroxide and (C) metal-doped thermosensitive titanium dioxide photocatalyst are mixed and used in a ratio of 3:1 to 1:3. In addition, in Examples 25 to 27 containing (A):(B):(C) at the same time, the components are mixed and used in a weight ratio of 1:1:1.

[0108] The remaining amount of solvent used was cellosolve acetate.

[0109] At this time, (C) metal-doped thermosensitive titanium dioxide photocatalyst is prepared by using titanium compound [Ti(i-OC3H7)4], isopropyl alcohol, nitric acid, manganese compound [Mn(NO3)2)], platinum compound [Pt(NH3)2], and methyltertiarymethylsilane.

[0110] In more detail, 5L of distilled water was added to the reactor, and 100ml of nitric acid and 20g of Mn(NO3)2 were dissolved, and then the temperature was heated to 80°C, and then 12.5g of platinum compound [Pt(NH3)2] was added and stirred. In another reactor, 1500g of titanium compound [Ti(i-OC3H7)4] and 150ml of isopropanol were mixed and added to the above solution. The mixed solution was cooled to room temperature, and then 10g of methyl tert-methylsilane was added, the resulting precipitate was filtered, and then dried at a temperature of 300°C to obtain the (C) metal-doped thermosensitive titanium dioxide photocatalyst.

[0111] [Table 1]

[0112]

[0113] For the prepared solution, as shown in [Table 2], the antiviral composite resin composition of the embodiment was roll-coated on a single-sided plated coating with a coating weight of 60 g / m 2 The Zn-Al-Mg ternary alloy-plated steel sheet or the alloy-plated steel sheet with a primer coating layer is coated so that the dry coating thickness is 15-20 μm, and then cooled after curing and drying at a metal peak temperature (PMT) of 232°C to manufacture antiviral composite resin-coated steel sheets with composite resin coatings as embodiments and comparative examples.

[0114] The primer coating layer is formed using a composition consisting of 50 wt % polyethylene polymer resin, 10 wt % melamine curing agent, 5 wt % colloidal silica, 5 wt % light yellow pigment and the remainder solvent, and the thickness of the formed dry coating film after drying is 5 μm.

[0115] The surface properties of the composite resin coated steel sheets having the composite resin coating obtained through the above-mentioned manufacturing process were evaluated, and the results are shown in [Table 2] and [Table 3].

[0116] [Table 2]

[0117]

[0118] [Table 3]

[0119]

[0120] The surface characteristics and evaluations of the above-mentioned [Table 2] and [Table 3] were performed by the following method.

[0121] <Thickness of coating film>

[0122] The thickness of the coating film was measured using a non-destructive portable coating thickness gauge.

[0123] <Design>

[0124] The color of the coating film was evaluated based on the color difference value compared with a beige standard sample and is shown below.

[0125] [Evaluation criteria] ◎: ΔE<1.0 (very good), ○: 1.0≤ΔE<1.5 (excellent), △: 1.5≤ΔE<2.5 (poor), ×: 2.5<ΔE (very bad)

[0126] <Gloss>

[0127] The evaluation was performed by measuring the 60° specular reflectance using an instrument from SHEEN.

[0128] <Pencil Hardness>

[0129] A 10 cm line was drawn at an angle of 45° under a load of 1000±10 g using a pencil (HB-4H) from Mitsubishi Corporation, and then the evaluation was performed by checking whether a scratch was generated.

[0130] <Evaluation of Corrosion Resistance>

[0131] The corrosion resistance is evaluated by the composite salt spray method (Cyclic Corrosion Test, CCT). The salt spray (concentration of 5%, spray pressure of 1kg / cm at 35°C) is carried out under the condition of 95% relative humidity. 2 The steel sheets were subjected to the following treatments: the steel sheets were subjected to the following treatments: 1) for 5 hours at a relative humidity of 30% and a temperature of 70°C for 2 hours, and then subjected to the following treatments at a relative humidity of 95% and a temperature of 50°C for 3 hours. The above process was regarded as one cycle, and the cycle was repeated 100 times. The area of ​​white rust generated on the surface of the steel sheets was then evaluated.

[0132] [Evaluation criteria] ◎: Corrosion area is 0%, ○: Corrosion area is less than 5%, △: Corrosion area is 5-30%, ×: Corrosion area is more than 30%

[0133] <Evaluation of Bending Workability>

[0134] For the antiviral composite resin coated steel plate, the surface of the steel plate was placed in a vise, bent 180° with a pressure of 1 kgf, and then pressed to become a flat surface (0T-bending). The evaluation was performed by whether cracks occurred on the surface peeled off by the tape when the film was peeled off after sticking a transparent tape on the bent film and whether the film was peeled off.

[0135] [Evaluation criteria] ◎: No cracks or peeling, ○: Fine cracks were visible but no peeling of the coating film occurred, △: Severe cracks occurred but no peeling of the coating film occurred, ×: Cracks occurred and peeling of the coating film occurred.

[0136] <Chemical resistance>

[0137] The determination was made based on the number of times the coating film peeled off when gauze soaked with methyl ethyl ketone (MEK) was rubbed back and forth with a load of 1 kg and a force of 1 kgf.

[0138] [Evaluation criteria] ◎: 100 times or more, ○: 70 times or more and less than 100 times, △: 40 times or more and less than 70 times, ×: less than 40 times.

[0139] <Antiviral properties>

[0140] <Evaluation of short-term antiviral activity>

[0141] The antiviral properties of the composite resin-coated steel sheets of the examples and comparative examples were evaluated at the Institute of Zoonotic Infectious Diseases of Chonbuk National University according to ISO 21702. 400 μL of COVID-19 (3.2×10 6 TCID50 / ml) virus stock solution was dropped onto the control group and composite resin coated steel plate test piece (50×50mm), covered with a polymer film (40×40mm, polyethylene film), and then left in contact at room temperature for 2 hours, and then recovered with 1.9mL of culture medium. The culture medium liquid was serially diluted until it reached 10 -1 Up to 10 -5 , and prepare a series of dilutions. Infect each smear with monkey host cells (Vero E6 Cell) and then culture at 37°C for 72 hours. Drop MTT staining solution (Triazolium) into each well, and then determine whether the host cells are alive by observing the color change. Calculate the concentration value of the live cells in the well ( TCID50 ), and the virus killing rate was quantitatively evaluated by comparison with the control group.

[0142] <Evaluation of long-term antiviral activity>

[0143] The composite resin-coated steel plate was irradiated under QUV-B evaluation conditions for 1000 hours, and then the antiviral property was evaluated by the same method as the evaluation of the short-term antiviral property.

[0144] [Evaluation criteria] ◎: 95% ≤ virus killing rate (X), ○: 90% ≤ virus killing rate (X) < 95%, △: 80% ≤ virus killing rate (X) < 90%, ×: virus killing rate (X) < 80%

[0145] In the antiviral composite resin coated steel plate of the present invention, it is known that when the antiviral composite resin composition is coated to a dry coating thickness of 15 μm, it has a beautiful appearance color itself, and therefore has excellent appearance design, but when a primer is included under the composite resin top coating, a more beautiful color is presented. It is judged that the above effect is due to the primer coating film as the bottom coating film. As the coating film thickness increases, the covering effect of the base steel plate increases, the diffuse reflection of light decreases, and the vividness of the color brought by the pigment increases.

[0146] In the antiviral composite resin coated steel plate of the present invention, the antiviral composite resin composition is also effective when (a) metal hydroxide or (b) hydroxyapatite is used alone, but when added together with (c) metal-doped thermosensitive titanium dioxide photocatalyst, the killing rate of viruses is greatly increased. It is judged that when droplets containing viruses adhere to the coating surface of the steel plate, the killing of viruses is promoted by the action of cations and anions generated by (a) metal hydroxide or (b) hydroxyapatite and the active oxygen generated under the action of (c) metal-doped thermosensitive titanium dioxide photocatalyst. In addition, in the evaluation of the long-term durability of the antiviral composite resin coated steel plate, the excellent result of no reduction in antiviral properties was also shown.

Claims

1. An antiviral composite resin composition, comprising: 30-60 wt % of a urethane modified polyester binder resin; 3-15 wt % of a curing agent; 0.1-10 wt% pigment; 0.1-10 wt% of an antiviral compound; and The remaining solvent, in, The antiviral compound comprises a metal hydroxide ([M1(OH)2]), a hydroxyapatite ([Ca 10 (PO4)6(OH)2]) and (C) metal-doped thermosensitive titanium dioxide photocatalyst ([M2-TiO2]), The M1 is Ca or Mg, The M2 is Pt, Cr, V, Mn, Fe, Zn, Cu, Ni, Zr, Mo, Ag, W or Au.

2. The antiviral composite resin composition according to claim 1, wherein The urethane-modified polyester binder resin has a weight average molecular weight (MW) of 2,000 to 30,000.

3. The antiviral composite resin composition according to claim 1, wherein The urethane-modified polyester binder resin has a hydroxyl value of 10 to 300.

4. The antiviral composite resin composition according to claim 1, wherein The acid value of the urethane-modified polyester binder resin is 5-30 mgKOH / g.

5. The antiviral composite resin composition according to claim 1, wherein The curing agent is one or more selected from aziridine curing agent, melamine curing agent and isocyanate curing agent.

6. The antiviral composite resin composition according to claim 5, wherein The isocyanate curing agent is one or more compounds selected from the group consisting of the following structural formula (d) and the following structural formula (e), (d) In the structural formula (d), R is methyl, ethyl, propyl, phenyl, 2-isopropylphenyl or cyclohexyl, (e) In the structural formula (e), R' is 1,3-phenylene, 1,4-phenylene, 2,4-tolylene, 2,6-tolylene, m-xylylene, 4,4'-dicyclohexylmethane, 4,4'-methylenediphenyl or hexamethylene.

7. The antiviral composite resin composition according to claim 1, wherein The pigment comprises at least one selected from ferric oxide (Fe2O3), titanium dioxide (TiO2), carbon black, carbon nanotubes, graphite and graphene.

8. The antiviral composite resin composition according to claim 1, wherein The average particle size of the pigment is 5-30 μm.

9. The antiviral composite resin composition according to claim 1, wherein The antiviral composite resin composition further comprises an anti-rust pigment, and the anti-rust pigment is one or more selected from colloidal silica, silica sol and alkali metal silicate.

10. The antiviral composite resin composition according to claim 1, wherein The antiviral compound is a combination of any one of the (A) metal hydroxide and the (B) hydroxyapatite and the (C) metal-doped thermosensitive titanium dioxide photocatalyst.

11. The antiviral composite resin composition according to claim 10, wherein The weight ratio of any one of the (A) metal hydroxide and the (B) hydroxyapatite in the antiviral compound to the (C) metal-doped thermosensitive titanium dioxide photocatalyst is 3:1 to 1:

3.

12. The antiviral composite resin composition according to claim 1, wherein The antiviral compound simultaneously comprises the (A) metal hydroxide, the (B) hydroxyapatite and the (C) metal-doped thermosensitive titanium dioxide photocatalyst.

13. The antiviral composite resin composition according to claim 12, wherein The weight ratio of the (A) metal hydroxide, the (B) hydroxyapatite and the (C) metal-doped thermosensitive titanium dioxide photocatalyst is 1:1:

1.

14. The antiviral composite resin composition according to claim 1, wherein The remaining solvent is one or more selected from toluene, xylene, isopropyl alcohol, solvent naphtha, cellosolve, cellosolve acetate and butyl cellosolve.

15. An antiviral composite resin coated steel plate, comprising: Base steel plate; as well as An antiviral composite resin coating film, wherein the antiviral composite resin coating film is located on at least one side of the base steel plate, and the antiviral composite resin coating film comprises the antiviral composite resin composition according to any one of claims 1 to 14.

16. The antiviral composite resin coated steel sheet according to claim 15, wherein: The basic steel sheet is a hot-dip galvanized steel sheet (GI), an alloyed hot-dip galvanized steel sheet (GA), an electro-galvanized steel sheet (EG), an aluminum-plated steel sheet or a zinc-aluminum-magnesium ternary alloy-plated steel sheet.

17. The antiviral composite resin coated steel sheet according to claim 15, wherein: The dry coating thickness of the antiviral composite resin coating is 3-40 μm.

18. The antiviral composite resin coated steel sheet according to claim 15, wherein: The antiviral composite resin coated steel plate further includes a primer coating between the base steel plate and the antiviral composite resin coating, and the primer coating is prepared by using a composition comprising 40-60 weight % of a polyethylene polymer resin, 5-15 weight % of a melamine curing agent, 1-8 weight % of colloidal silica, 1-8 weight % of a pigment and a balance of a solvent.

19. The antiviral composite resin coated steel sheet according to claim 18, wherein: The dry coating thickness of the primer coating is 2-7 μm.

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